US20140011089A1 - Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method - Google Patents

Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method Download PDF

Info

Publication number
US20140011089A1
US20140011089A1 US14/006,258 US201214006258A US2014011089A1 US 20140011089 A1 US20140011089 A1 US 20140011089A1 US 201214006258 A US201214006258 A US 201214006258A US 2014011089 A1 US2014011089 A1 US 2014011089A1
Authority
US
United States
Prior art keywords
cycle
polyimide precursor
mah
active substance
precursor solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US14/006,258
Other languages
English (en)
Inventor
Hiroshi Yamada
Kazuki Sawa
Yoshihito Nimura
Yuusuke Eda
Yasue Okuyama
Takuhiro Miyuki
Tetsuo Sakai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IST Corp Japan
National Institute of Advanced Industrial Science and Technology AIST
IST Corp USA
Original Assignee
IST Corp Japan
National Institute of Advanced Industrial Science and Technology AIST
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IST Corp Japan, National Institute of Advanced Industrial Science and Technology AIST filed Critical IST Corp Japan
Assigned to I.S.T. CORPORATION, NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY reassignment I.S.T. CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SAKAI, TETSUO, EDA, Yuusuke, MIYUKI, TAKUHIRO, OKUYAMA, Yasue, NIMURA, Yoshihito, SAWA, KAZUKI, YAMADA, HIROSHI
Publication of US20140011089A1 publication Critical patent/US20140011089A1/en
Priority to US15/813,734 priority Critical patent/US20180076461A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to polyimide precursor solutions and polyimide precursors.
  • the present invention relates to polyimide resins obtained from polyimide precursor solutions or polyimide precursors.
  • the present invention relates to mixture slurries that contain active substance particles in a polyimide precursor solution, particularly mixture slurries for use in forming an anode. Additionally, the present invention relates to methods for producing these mixture slurries.
  • the present invention relates to electrodes (anodes) obtained from these mixture slurries. Furthermore, the present invention relates to methods for forming these electrodes.
  • This monomeric polyimide precursor comprises mainly a tetracarboxylic acid ester compound and a diamine compound that, for example, upon heating forms a porous structure by undergoing high-molecular-weight polymerization via imidization.
  • the monomeric polyimide precursor By undergoing high-molecular-weight polymerization, the monomeric polyimide precursor becomes firmly bound to the active substance particles and current collector body, and adding this monomeric polyimide precursor to an anode mixture slurry can adequately prevent the loosening and detachment of the active substance layer from the anode current collector body due to expansion and contraction of the active substance particles. Furthermore, by forming a porous structure, a solid template (mold) is formed that encloses the active substance, and when the active substance particles bind strongly in the boreholes, the porous structure is maintained without collapse even after repeated intense expansion and contraction by the active substance particles, and consequently it is possible for the charge/discharge cycle in lithium ion secondary batteries to be increased dramatically.
  • the problem to be solved in the present invention is to provide a polyimide precursor and a polyimide precursor solution that can bind the active substance particles and the current collector body more strongly, and a mixture slurry that can further increase the charge/discharge cycle in lithium ion secondary batteries and the like.
  • a polyimide precursor solution relating to a first aspect of the present invention contains a tetracarboxylic acid ester compound, a diamino compound having anionic groups, and a solvent.
  • the tetracarboxylic acid ester compound and the diamino compound are dissolved in this solvent.
  • the tetracarboxylic acid ester compound is preferably an aromatic tetracarboxylic acid ester compound. Moreover, the tetracarboxylic acid ester compound is preferably an aromatic tetracarboxylic acid diester compound.
  • the tetracarboxylic acid ester compound can be obtained extremely simply via esterification of the corresponding tetracarboxylic acid dianhydride in alcohol. Furthermore, the esterification of the tetracarboxylic acid dianhydride is preferably carried out at a temperature of 50° C. or above and 150° C. or below.
  • examples of alcohols that can form a tetracarboxylic acid ester compound include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, cyclohexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol, 2-(isopropoxy)ethanol, 2-butoxyethanol, phenol, 1-hydroxy-2-propanone, 4-hydroxy-2-butanone, 3-hydroxy-2-butanone, 1-
  • tetracarboxylic acid ester compounds can be constructed by other methods, for example, by direct esterification of tetracarboxylic acids.
  • 3,3′,4,4′-benzophenonetetracarboxylic acid diester is particularly preferred.
  • the diamino compound is preferably an aromatic diamino compound.
  • anionic functional groups include carboxyl groups, sulfate ester groups, sulfonic acid groups, phosphoric acid groups, phosphate ester groups, and the like.
  • carboxyl group is particularly preferred.
  • diamino compounds include 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, meta-phenylenediamine-4-sulfonic acid, and the like.
  • the polyimide precursor solution relating to the present aspect can include diamine compounds that do not have anionic groups.
  • diamine compounds that do not have anionic groups include para-phenylene diamine (PPD), meta-phenylene diamine (MPDA), 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane (MDA), 2,2-bis-(4-aminophenyl)propane, 3,3′-diaminodiphenylsulfone (33DDS), 4,4′-diaminodiphenylsulfone (44DDS), 3,3′-diaminodiphenyl
  • the molar ratio for the tetracarboxylic acid ester compound and the diamine compound is usually within the range of 55:45 to 45:55. Furthermore, the abovementioned molar ratio for the tetracarboxylic acid ester compound and the diamine compound can be suitably changed to a ratio different from that described above provided that the scope of the present invention is not compromised.
  • the solvent dissolves the tetracarboxylic acid ester compound and the diamino compound.
  • the solvent include preferably the type of alcohol used to form the abovementioned tetracarboxylic acid ester.
  • N-methyl-2-pyrrolidone, dimethylacetamide, aromatic hydrocarbons, and the like can be added to this solvent.
  • conductive fillers, dispersing agents, and the like can be included in the polyimide precursor mixture.
  • Conductive fillers function as conductive additives.
  • Examples of such conductive fillers include carbon black (oil furnace black, channel black, lamp black, thermal black, Ketjen black, acetylene black, and the like), carbon nanotubes, carbon nanofibers, fullerenes, carbon microcoils, graphite (natural graphite, artificial graphite, and the like), carbon black and carbon fiber short fiber (PAN carbon short fiber, pitch carbon fiber short fiber, and the like), and the like.
  • Such conductive fillers can be used singly or in combinations.
  • a dispersing agent is added to make a uniform dispersion of the active substance particles in the mixture slurry.
  • examples of such dispersing agents include sorbitan monooleate, N,N-dimethyllaurylamine, N,N-dimethylstearylamine, N-(coco alkyl)-1,3-diaminopropane, and the like. Furthermore, such dispersing agents can be used singly or in combinations.
  • the conductive fillers to be uniformly dispersed in the polyimide precursor solutions that contain such conductive fillers, it is preferable for them to be adequately kneaded in a kneading machine such as a roller mill, attritor, ball mill, pebble mill, sand mill, Kady mill, Mechano-Fusion, stone mill, or the like.
  • a kneading machine such as a roller mill, attritor, ball mill, pebble mill, sand mill, Kady mill, Mechano-Fusion, stone mill, or the like.
  • the polyimide precursor solution relating to the first aspect furthermore contains active substance particles.
  • active substance particles examples include silicon (Si) particles, silicon oxide (SiO) particles, silicon alloy particles, tin (Sn) particles, or the like.
  • Examples of silicon alloys include solid solutions of silicon with one or more other elements, intermetallic compounds of silicon with one or more other elements, eutectic alloys of silicon with one or more other elements, and the like.
  • Examples of methods for preparing silicon alloys include the arc fusion method, liquid quenching method, mechanical alloying method, sputtering method, chemical vapor deposition method, calcining method, and the like.
  • examples of the liquid quenching method include the single roller method, the double roller method, and various kinds of atomizer methods such as the gas atomizer method, water atomizer method, disk atomizer method, and the like.
  • the active substance particles can be core-shell type active substance particles in which the aforementioned active substance particles are coated with a metal or the like.
  • Such core-shell type active substance particles can be manufactured using an electroless deposition method, electrolytic method, chemical reduction method, evaporation method, sputtering method, chemical vapor deposition method, or the like.
  • the shell part is preferably formed from the same metal used to form the current collector body. The calcining of such active substance particles greatly increases their bonding ability toward the current collector body, and can provide superior charge/discharge cycle characteristics.
  • the active substance particles can also include materials to be alloyed with lithium. Examples of such materials include germanium, tin, lead, zinc, magnesium, sodium, aluminum, gallium, indium, alloys thereof, and the like.
  • the active substance particles can undergo surface treatment with a silane coupling agent. If active substance particles are treated in this manner, along with the active substance particles being well dispersed in the mixture slurry, the active substance binding ability toward polyimide resin can be increased.
  • the active substance particles preferably have an average particle diameter of 0.5 ⁇ m or greater and less than 20 ⁇ m, and more preferably 0.5 ⁇ m or greater and less than 10 ⁇ m.
  • said average particle diameter is measured by a laser diffraction/scattering method using a Microtrac MT3100II, particle diameter distribution measuring apparatus (Nikkiso Co., Ltd.). Additionally, the absolute value of the expansion/contraction of the active substance particle volume associated with the absorption/desorption of lithium in the charging-discharging reaction becomes smaller when active substance particles with a smaller average particle diameter are used.
  • the absolute amount of distortion between the active substance particles within the electrodes during the charging-discharging reaction also becomes smaller. Consequently, no destruction of the polyimide resin template occurs, deterioration of the current collection properties of the electrode is suppressed, and it is possible to obtain good charging and discharging characteristics.
  • the particle size distribution of the active substance particles it is preferable for the particle size distribution of the active substance particles to be as narrow as possible. If the particle size distribution is broad, there will be significant differences in size between the active substance particles, and since significant absolute differences will be present in the expansion/contraction in the volume associated with the absorption/desorption of lithium, distortions will occur within the active substance layers, and there is increased concern that destruction of the polyimide resin template will occur.
  • the active substance particles are present in a dispersed state in the polyimide precursor varnish comprising primarily a tetracarboxylic acid ester compound, a diamino compound with anionic groups, and a solvent.
  • the active substance particles relating to this aspect are the active substance particles used for anodes in the nonaqueous secondary batteries among lithium ion secondary batteries.
  • a polyimide precursor relating to a third aspect of the present invention contains a tetracarboxylic acid ester compound, and a diamino compound having anionic groups.
  • the “tetracarboxylic acid ester compound” and “diamino compound having anionic groups” are the same “tetracarboxylic acid ester compound” and “diamino compound having anionic groups” as described in the first aspect.
  • the polyimide precursor can also contain the abovementioned conductive fillers and dispersing agents. Such polyimide precursors can be obtained by mixing together the “tetracarboxylic acid ester compound” and “diamino compound having anionic groups”, and can also be obtained by drying the abovementioned polyimide precursor solution.
  • the “tetracarboxylic acid ester compound” and “diamino compound having anionic groups” can be in solution form or in powder form.
  • a polyimide resin relating to a fourth aspect of the present invention can be obtained by heating the polyimide precursor solution relating to the first aspect, or by heating the polyimide precursor relating to the third aspect.
  • a polyimide resin relating to a fifth aspect of the present invention that is the polyimide resin relating to the fourth aspect with a glass transition temperature of 300° C. or higher.
  • a polyimide resin relating to a sixth aspect of the present invention that is the polyimide resin relating to either the fourth or fifth aspect having a molecular weight between crosslinks of 30 or less.
  • the molecular weight between crosslinks is preferably 20 or less, and further preferably 10 or less.
  • the molecular weight between crosslinks is smaller, three-dimensional crosslinks will appear. The molecular weight between crosslinks is an important factor for studying the point binding of the adherend.
  • a polyimide resin relating to a seventh aspect of the present invention is the polyimide resin relating to any one of the fourth through sixth aspects having amide groups.
  • An electrode relating to an eighth aspect of the present invention is equipped with a current collector body and an active substrate layer.
  • the current collector body is preferably a conductive metal foil.
  • a conductive metal foil can be formed from a metal such as copper, nickel, iron, titanium, cobalt, or the like, or can be formed from an alloy obtained from combinations of such metals.
  • surface roughening of the current collector body can also be carried out by providing electrolytic copper or an electrolytic copper alloy on the surface of the foil.
  • surface roughening of the current collector body can also be carried out by using a surface roughening treatment. Examples of such surface roughening treatments include vapor phase epitaxy, etching, grinding, and the like. Examples of vapor phase epitaxy methods include the sputtering method, CVD method, chemical vapor deposition method, and the like. Examples of etching methods include the physical etching method, chemical etching method, and the like. Examples of grinding methods include grinding with sandpaper, grinding by the blast method, and the like.
  • an undercoat layer can be formed on the current collector body.
  • the undercoat layer is preferably formed from a resin that can adhere well to the polyimide resin and a conductive filler that imparts conductivity to the undercoat.
  • the undercoat layer is preferably formed by a chemical dispersing a conductive filler into the abovementioned monomeric polyimide precursor solution, or a chemical dispersing a conductive filler into a polyamic acid polyimide precursor solution.
  • examples of conductive fillers include carbon black (oil furnace black, channel black, lamp black, thermal black, Ketjen black, acetylene black, and the like), carbon nanotubes, carbon nanofibers, fullerenes, carbon microcoils, graphite (natural graphite, artificial graphite, and the like), conductive potassium titanate whisker, filamentary nickel, carbon fiber short fiber (PAN carbon short fiber, pitch carbon fiber short fiber, and the like), whicker fibers, metal particles (copper particles, tin particles, nickel particles, silver particles, and the like), metal oxides (titanium dioxide, tin dioxide, zinc dioxide, nickel oxide, copper oxide, and the like), metal carbides (titanium carbide, silicon carbide, and the like), and the like. These conductive fillers can be used singly or in combinations.
  • the abovementioned mixture slurry When an undercoat layer is formed on the current collector body as described above, it is preferable to apply the abovementioned mixture slurry after the “polyimide resin solution with conductive filler” used to form the undercoat layer undergoes heating at a sufficient temperature between 50° C., and 100° C. for several tens of minutes. If done in this manner, the abovementioned mixture slurry will be applied when the undercoat layer is not yet completely in a solidified state, which will give good adhesion between the undercoat layer and the active substance layer.
  • the current collector body relating to this aspect is a current collector body used for anodes in non-aqueous secondary batteries such as lithium ion secondary batteries, and so on.
  • the active substance layer is obtained from the abovementioned mixture slurry.
  • this active substance layer is coated onto the current collector body.
  • the active substance layer is formed on the current collector body.
  • this active substance layer is primarily composed of active substance particles and polyimide resin.
  • the polyimide resin in this active substance layer has a porous structure, which functions as a template material to enclose the active substances, and along with binding the active substance particles within these pores, it plays a role in the binding between the active substance particles and the current collector body.
  • the polyimide resin will generally have a porosity in the range of from 20 parts by volume to 40 parts by volume.
  • this polyimide resin will have anionic groups.
  • the polyimide resin will primarily be formed from units derived from a tetracarboxylic acid and units derived from a diamine. Thus, as mentioned above, the anionic groups are bonded to the diamine-derived units.
  • this coating can be calcined. Furthermore, it is preferable for the calcining of the coating to be conducted under a non-oxidizing atmosphere such as a vacuum, a nitrogen atmosphere, an argon atmosphere, or the like, or under a reducing atmosphere such as a hydrogen atmosphere, or the like.
  • the calcining temperature is preferably at or above the temperature at which the monomeric polyimide precursor in the above-described mixture slurry will become a suitably high-molecular-weight polymer through imidization, and at or below the melting point of current collector body and the active substance particles.
  • the recommended calcining temperature for the mixture slurry relating to the present aspect is between 100° C. and 400° C. Furthermore, the calcining temperature for this mixture slurry is more preferably between 100° C. and 300° C., still further preferably between 150° C. and 300° C., and still further preferably between 200° C. and 300° C. Along with avoiding deterioration of the current collector body due to heat, this serves to preserve the crosslinked structure of the polyimide resin.
  • Examples of calcining methods include the use of a common constant temperature oven, plasma discharge sintering, the hot press method, and the like. By using such methods to form the active substance layer on the current collector body or the undercoat layer, the porous polyimide layer provides strong binding not only mutually between the active substance particles in the active substance layer, but also between the active substance particles and the current collector body.
  • this coating can be rolled together with the current collector body, or the rolling can be omitted, but it is preferable to omit the rolling. Furthermore, if the “packing density of the active substance particles in the coating”, the “adhesiveness between active substance particles”, or the “adhesiveness between active substance particles and the current collector body” becomes excessively high when the coating and the current collector body are rolled, this will decrease the lifetime of the charging/discharging cycle. On the other hand, if the rolling is not done, this avoids damaging the current collector body or the polyimide resin template, with the result that good charging/discharging cycle properties will be obtained.
  • the polyimide resin content in the active substance layer is preferably 5 wt % or more and 50 wt % or less based on the total weight of the active substance layer, more preferably 5 wt % or more and 30 wt % or less, and further preferably 5 wt % or more and 20 wt % or less.
  • the volume content of the polyimide resin in the active substance layer is preferably 5 vol % or more and 50 vol % or less based on the total volume of the active substance layer.
  • the polyimide content in the active substance layer is less than 5 wt % or 5 vol %, there will be insufficient mutual adhesion between the active substance particles or insufficient adhesion between the active substance particles and the current collector body, and if the polyimide content in the active substance layer exceeds 50 wt % or 50 vol %, the resistance within the electrode will increase and the initial charging might be difficult.
  • the method for producing a mixture slurry relating to a ninth aspect of the present invention has a first mixing step and a second mixing step.
  • a polyimide precursor solution with carbon black is prepared by mixing carbon black into monomeric polyimide precursor solution so as not to apply the shear stress substantially.
  • the expression “so as not to apply the shear stress substantially” means that a degree of shear stress is permissible only if no damage to the carbon black fibers occurs.
  • the monomeric polyimide precursor solution contains a tetracarboxylic acid ester compound, a diamine compound having anionic groups, and a solvent. Furthermore, the tetracarboxylic acid ester compound and the diamino compound are dissolved in the solvent.
  • a mixture slurry is prepared by mixing active substance particles into the polyimide precursor solution with carbon black. Furthermore, based on 100 parts by weight of the active substance particles, the solids fraction of the monomeric polyimide precursor solution is preferably within the range from 5 parts by weight to 11 parts by weight.
  • the method for producing an electrode relating to a tenth aspect of the present invention has a coating step and the heating step.
  • the coating step the abovementioned mixture slurry is coated onto a current collector body to form a mixture slurry coating on the current collector body. Furthermore, an undercoat layer can already have been formed on the current collector body.
  • the mixture slurry coating is heated to form a porous active substance layer.
  • the mixture slurry coating is preferably heated to a temperature of 100° C. or above and less than 400° C., and is further preferably heated to a temperature of 150° C. or above and less than 350° C.
  • the active substance layer and current collector body are usually rolled when the electrode is formed.
  • a porous active substance layer is formed from the mixture slurry in this electrode formation method.
  • the active substance layer is not rolled in this electrode formation method.
  • the polyimide resin in the active substance layer is made porous, and the active substance particles are enclosed in the polyimide resin that has been made porous. For this reason, the active substance particles are unlikely to fall out of the polyimide resin even with repeated intense expansion and contraction by the active substance particles.
  • the mixture slurry coating is heated at a relatively low temperature in this electrode formation method.
  • the polyimide resin can be relatively flexible if this electrode formation method is utilized. Consequently, it will be easier for the polyimide resin to accommodate the expansion of the active substance particles if this electrode formation method is utilized, and the active substance particles can be prevented from falling out of the polyimide resin.
  • the polyimide precursor solution and the polyimide precursor relating to the present invention can provide stronger binding (in particular, point binding) between the active substance particles and the current collector body compared to conventional polyimide precursor solutions and polyimide precursor. And when the polyimide precursor solutions and polyimide precursor are utilized as a binder for the anode active substance layer in a lithium ion secondary battery, further improved charging/discharging cycle times are expected for lithium ion secondary batteries and the like.
  • the polyimide precursor solution and the polyimide precursor relating to the present invention are utilized as a binder for the active substance particles, not only can stronger binding (in particular, point binding) between the active substance particles and the current collector body be expected, but also promotion of the uptake of cations (lithium ions and the like) by the free carboxyl groups, which can improve the discharge capacity of lithium ion secondary batteries and the like.
  • FIG. 1 is a chart of measurements using Fourier transform infrared (FT-IR) spectroscopy on strips of polyimide film relating to Working Example 1 of the present invention and Comparative Example 1.
  • FT-IR Fourier transform infrared
  • FIG. 2 is a chart of dynamic viscoelasticity measurements of strips of polyimide film relating to Working Example 1 of the present invention and Comparative Example 1.
  • the synthesis vessel was a 500 mL 3-neck flask equipped with a stirring shaft that was fitted with a polytetrafluoroethylene stir paddle. Then, after this synthesis vessel was charged with 10.19 g (0.032 mol) 3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride (Daicel Chemical Industries, BTDA), and 2.91 g (0.063 mol) ethanol (Ueno Chemical Industries, Ltd.), the synthesis vessel contents were heated to 90° C. with stirring for 1 hr to prepare a BTDA diester solution as a polyimide precursor solution with a solids fraction of 28 wt %. After the BTDA diester solution was cooled to 45° C.
  • BTDA 3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride
  • Ueno Chemical Industries, Ltd. the synthesis vessel contents were heated to 90° C. with stirring for 1 hr to prepare a BTDA diester solution
  • the thickness of the prepared dried anode intermediate after drying was 19 ⁇ m.
  • the anode intermediate was cut into circular shapes with a diameter of 11 mm, and underwent heat treatment at 300° C. for 1 hr (calcining) under a nitrogen atmosphere to prepare a calcined anode.
  • the counter electrode was prepared by cutting lithium metal foil (thickness: 0.5 mm) into circular shapes with a diameter of 13 mm.
  • a mixture of ethylene carbonate and diethyl carbonate in a ratio of 1:1 (v/v) was prepared, and LiPF 6 was dissolved therein to give 1 mole/L, and this was used as the nonaqueous electrolyte.
  • the anode, counter electrode, and nonaqueous solvent prepared as mentioned above were combined inside a CR2032SUS coin cell to prepare the lithium ion secondary battery.
  • the cathode and counter electrode were arranged to face each other via a polypropylene separator (Celgard 2400, Celgard Co.) reinforced with glass fiber fabric.
  • this piece of polyimide film was placed in an FTIR-8400 instrument (Shimadzu Corp.), and the FT-IR measurement was carried out using the thin-film transmission method.
  • confirmation came from the peaks in the vicinity of 3350 cm ⁇ 1 and 3100 cm ⁇ 1 belonging to the unassociated and associated amide group N-H stretching modes, respectively. (see FIG. 1 ). Consequently, the presence of amide groups in this piece of polyimide film was confirmed. Therefore, it was presumed that the carboxyl groups of the diaminobenzoic acid were converted to amide groups by heating.
  • the storage elastic modulus was measured at a frequency of 1 Hz and a temperature program of 2° C./min to obtain the storage elastic modulus curve for this piece of polyimide film.
  • the glass transition temperature (T g ) for this piece of polyimide film was the temperature that corresponds to the intersection point between “an extrapolation from the low-temperature, straight-line portion of the storage modulus curve”, and “the tangential line at the point considered to have the maximum slope in the glass transition region of the curve”.
  • the glass transition temperature (T g ) for this piece of polyimide film was 339° C.
  • the sanded surface of this copper foil was coated with the abovementioned monomeric polyimide precursor solution to have a film thickness value of between approximately 10 ⁇ m and 20 ⁇ m after calcining.
  • this monomeric polyimide precursor solution was dried under an air atmosphere for 10 min at 100° C., it was heated to 220° C. under reduced pressure for 1 hr, then calcined at 250° C. under an air atmosphere for 1 hr, and then at 275° C. for 1 hr to give the test piece.
  • the adhesion strength of the polyimide resin toward copper foil was measured according to the “General Rules of Coating Films for Automobile Parts 4.15, cross-cut adhesion test method (JIS D0202 (1998))”. Furthermore, “Askul cellophane tape” from the Askul Co. was used for the cellophane tape. The result was that the adhesion strength of the polyimide resin toward copper foil was 28/100.
  • this sanded surface of this silicon wafer was coated with the abovementioned monomeric polyimide precursor solution to have a film thickness value of between approximately 10 ⁇ m and 30 ⁇ m after calcining
  • this monomeric polyimide precursor solution was dried under an air atmosphere for 10 min at 100° C., it was heated to 220° C. under reduced pressure for 1 hr, then calcined at 250° C. under an air atmosphere for 1 hr, and then at 275° C. for 1 hr to give the test piece.
  • the adhesion strength of the polyimide resin toward silicon wafer was measured according to the “General Rules of Coating Films for Automobile Parts 4.15, cross-cut adhesion test method (JIS D0202 (1998))”. Furthermore, “Askul cellophane tape” from the Askul Co. was used for the cellophane tape. The result was that the adhesion strength of the polyimide resin toward the silicon wafer was 100/100.
  • a charging/discharging cycle test was carried out on the lithium ion secondary battery.
  • the charging/discharging cycle test was carried out for 50 charging/discharging cycles at an ambient temperature of 30° C., charging/discharging rate of 0.1 C, a voltage cut-off of 0.0 V while charging and 1.0 V while discharging, and the discharge capacity in mAh/g was measured every cycle. Additionally, the maintenance factor was determined as the “ratio of the discharge capacity for the 30 th cycle to the discharge capacity for the 2 nd cycle” and “ratio of the discharge capacity for the 50 th cycle to the discharge capacity for the 2 nd cycle”. Furthermore, the specific capacity of the electrode surface of this lithium ion secondary battery was 4.62 mAh/cm 2 (see Table 1).
  • the discharge capacity was 4309.6 mAh/g for the 1 st cycle, 3584.8 mAh/g for the 2 nd cycle, 3115.0 mAh/g for the 30 th cycle, and 2689.8 mAh/g for the 50 th cycle.
  • a battery was prepared in the same manner as for Working Example 1, and its charging/discharging cycle characteristics were measured in the same manner as for Working Example 1. Furthermore, the specific capacity of the electrode surface of this lithium ion secondary battery was 4.70 mAh/cm 2 (see Table 2).
  • the discharge capacity was 4194.7 mAh/g for the 1 st cycle, 3470.1 mAh/g for the 2 nd cycle, 3026.7 mAh/g for the 30 th cycle, and 2614.1 mAh/g for the 50 th cycle.
  • the discharge capacity was 4238.8 mAh/g for the 1 st cycle, 3500.8 mAh/g for the 2 nd cycle, 3014.6 mAh/g for the 30 th cycle, and 2601.3 mAh/g for the 50 th cycle.
  • the discharge capacity was 4121.4 mAh/g for the 1 st cycle, 3414.3 mAh/g for the 2 nd cycle, 2945.5 mAh/g for the 30 th cycle, and 2544.7 mAh/g for the 50 th cycle.
  • the respective discharge capacity was 4144.9 mAh/g for the 1 st cycle, 3412.6 mAh/g for the 2 nd cycle, 2959.5 mAh/g for the 30 th cycle, and 2531.3 mAh/g for the 50 th cycle.
  • the discharge capacity was 4425.8 mAh/g for the 1 st cycle, 3843.5 mAh/g for the 2 nd cycle, 3364.5 mAh/g for the 30 th cycle, and 3021.8 mAh/g for the 50 th cycle.
  • the discharge capacity was 3541.5 mAh/g for the 1 st cycle, 3076.5 mAh/g for the 2 nd cycle, 3026.4 mAh/g for the 10 th cycle, 2803.4 mAh/g for the 30 th cycle, and 2424.6 mAh/g for the 50 th cycle.
  • the discharge capacity was 4700.7 mAh/g for the 1 st cycle, 4124.8 mAh/g for the 2 nd cycle, 3401.5 mAh/g for the 30 th cycle, and 2955.6 mAh/g for the 50 th cycle.
  • the discharge capacity was 3898.5 mAh/g for the 1 st cycle, 3384.8 mAh/g for the 2 nd cycle, 2997.9 mAh/g for the 30 th cycle, and 2559.5 mAh/g for the 50 th cycle.
  • the discharge capacity was 4282.7 mAh/g for the 1 st cycle, 3748.8 mAh/g for the 2 nd cycle, 3113.2 mAh/g for the 30 th cycle, and 2704.6 mAh/g for the 50 th cycle.
  • the discharge capacity was 3714.4 mAh/g for the 1 st cycle, 3231.6 mAh/g for the 2 nd cycle, 2835.7 mAh/g for the 30 th cycle, and 2405.2 mAh/g for the 50 th cycle.
  • the discharge capacity was 4424.0 mAh/g for the 1 st cycle, 3873.1 mAh/g for the 2 nd cycle, 3226.9 mAh/g for the 30 th cycle, and 2686.3 mAh/g for the 50 th cycle.
  • the discharge capacity was 3870.7 mAh/g for the 1 st cycle, 3391.8 mAh/g for the 2 nd cycle, 2977.3 mAh/g for the 30 th cycle, and 2524.6 mAh/g for the 50 th cycle.
  • the maintenance factors in this working example were determined as the “ratio of the discharge capacity for the 10 th cycle to the discharge capacity for the 2 nd cycle” and “ratio of the discharge capacity for the 30 th cycle to the discharge capacity for the 2 nd cycle”. Furthermore, the specific capacity of the electrode surface of this lithium ion secondary battery was 2.07 mAh/cm 2 (see Table 4).
  • the discharge capacity was 4448.6 mAh/g for the 1 st cycle, 3820.2 mAh/g for the 2 nd cycle, 3738.1 mAh/g for the 10 th cycle, and 3448.6 mAh/g for the 30 th cycle.
  • the maintenance factors in this working example were determined as the “ratio of the discharge capacity for the 10 th cycle to the discharge capacity for the 2 nd cycle”. Furthermore, the specific capacity of the electrode surface of this lithium ion secondary battery was 1.67 mAh/cm 2 (see Table 4).
  • the discharge capacity was 3736.7 mAh/g for the 1 st cycle, 3195.2 mAh/g for the 2 nd cycle, and 3083.1 mAh/g for the 10 th cycle.
  • the maintenance factor was determined in this working example as the “ratio of the discharge capacity after 10 cycles to the discharge capacity after 2 cycles”. Furthermore, the specific capacity of the electrode surface of this lithium ion secondary battery was 1.49 mAh/cm 2 (see Table 4).
  • the discharge capacity was 4022.2 mAh/g for the 1 st cycle, 3490.8 mAh/g for the 2 nd cycle, and 3441.9 mAh/g for the 10 th cycle.
  • the polyimide resin obtained from the abovementioned monomeric polyimide precursor solution had a glass transition temperature of 308° C., a molecular weight between crosslinks of 181, and an adhesion strength toward copper foil of 0/100. Furthermore, this polyimide resin had a weaker adhesion strength, and had already delaminated by the time it was cut into a grid pattern with a cutter knife.
  • the adhesion strength of the polyimide resin toward silicon wafer was measured according to the “General Rules of Coating Films for Automobile Parts 4.15, cross-cut adhesion test method (JIS D0202 (1998))”. Furthermore, “Askul cellophane tape” from the Askul Co. was used for the cellophane tape. The result was that the adhesion strength of the polyimide resin toward the silicon wafer was 100/100.
  • Example 1 Peaks in the vicinity of 3350 cm ⁇ 1 , 3100 cm ⁇ 1 Present Absent Glass transition temperature [T g ] (° C.) 339 308 Molecular weight between crosslinks [M x ] 2.9 181 Cross-cut adhesion strength 28/100 0/100 Adhesion strength toward a silicon wafer 100/100 100/100 (reference example)
  • the discharge capacity was 3533.4 mAh/g for the 1 st cycle, 2661.4 mAh/g for the 2 nd cycle, 1453.3 mAh/g for the 30 th cycle, and 1067.3 mAh/g for the 50 th cycle.
  • the discharge capacity was 3410.2 mAh/g for the 1 st cycle, 2757.5 mAh/g for the 2 nd cycle, 1207.2 mAh/g for the 30 th cycle, and 762.8 mAh/g for the 50 th cycle.
  • the discharge capacity was 3780.1 mAh/g for the 1 st cycle, 2709.1 mAh/g for the 2 nd cycle, 1202.9 mAh/g for the 30 th cycle, and 825.3 mAh/g for the 50 th cycle.
  • the discharge capacity was 3724.5 mAh/g for the 1 st cycle, 2911.2 mAh/g for the 2 nd cycle, 1860.4 mAh/g for the 30 th cycle, and 1410.8 mAh/g for the 50 th cycle.
  • the discharge capacity was 3431.7 mAh/g for the 1 st cycle, 2629.7 mAh/g for the 2 nd cycle, 1036.1 mAh/g for the 30 th cycle, and 746.9 mAh/g for the 50 th cycle.
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Mixture slurry TCE BTDA BTDA BTDA BTDA BTDA BTDA BTDA BTDA BTDA DAm 3,5-DABA 3,5-DABA 3,5-DABA 3,5-DABA 3,5-DABA 3,5-DABA Calcining conditions 1 hr @ 1 hr @ 4 hr @ 4 hr @ 4 hr @ 10 hr @ 300° C. 300° C. 350° C. 350° C. 350° C. 200° C.
  • Example 12 Mixture slurry TCE BTDA BTDA BTDA BTDA BTDA BTDA BTDA BTDA BTDA DAm 3,5-DABA 3,5-DABA 3,5-DABA 3,5-DABA 3,5-DABA Calcining conditions 10 hr @ 1 hr @ 1 hr @ 4 hr @ 4 hr @ 1 hr @ 200° C. 300° C. 300° C. 350° C. 350° C. 400° C.
  • Example 16 Mixture slurry TCE BTDA BTDA BTDA BTDA BTDA DAm 3,5-DABA 3,5-DABA 3,5-DABA 3,5-DABA Calcining conditions 1 hr @ 1 hr @ 10 hr @ 10 hr @ 400° C. 300° C. 200° C. 200° C.
  • Example 7 Mixture slurry TCE BTDA BTDA BTDA BTDA BTDA BTDA DAm m-PDA m-PDA m-PDA m-PDA m-PDA m-PDA Calcining conditions 1 hr @ 1 hr @ 1 hr @ 4 hr @ 4 hr @ 4 hr @ 300° C. 300° C. 300° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C. 350° C.
  • the monomeric polyimide precursor solution relating to the present invention clearly can more strongly bind the active substance particles to the current collector body, and by extension, along with being able to further improve the charging/discharging cycle in a lithium ion secondary battery, can increase the discharge capacity of a lithium ion secondary battery.
  • polyimide precursor solution and polyimide precursor relating to the present invention can be used to bind together active substance particles and a current collector body more strongly than a conventional polyimide precursor solution and polyimide precursor, they are a useful binder for the active substance layer on the anode of a lithium ion secondary battery.
  • the mixture slurry relating to the present invention can increase the discharge capacity of a lithium ion secondary battery or the like, it is useful as an anode mixture slurry for forming an anode active substance layer in nonaqueous secondary batteries such as lithium ion secondary batteries or the like.
  • polyimide precursor solution and polyimide precursor relating to the present invention are expected to exhibit good adhesion not only for active substance particles and current collector bodies but also toward other adherends, they can also be considered as heat-resistant adhesive agents.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US14/006,258 2011-03-25 2012-03-26 Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method Abandoned US20140011089A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/813,734 US20180076461A1 (en) 2011-03-25 2017-11-15 Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2011-068608 2011-03-25
JP2011-068595 2011-03-25
JP2011068595 2011-03-25
JP2011068608 2011-03-25
PCT/JP2012/002092 WO2012132396A1 (fr) 2011-03-25 2012-03-26 Solution précurseur de polyimide, précurseur de polyimide, résine polyimide, suspension épaisse mixte, électrode, procédé de production de la suspension épaisse mixte, et procédé de formation d'une électrode

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/002092 A-371-Of-International WO2012132396A1 (fr) 2011-03-25 2012-03-26 Solution précurseur de polyimide, précurseur de polyimide, résine polyimide, suspension épaisse mixte, électrode, procédé de production de la suspension épaisse mixte, et procédé de formation d'une électrode

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/813,734 Continuation US20180076461A1 (en) 2011-03-25 2017-11-15 Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method

Publications (1)

Publication Number Publication Date
US20140011089A1 true US20140011089A1 (en) 2014-01-09

Family

ID=46930172

Family Applications (2)

Application Number Title Priority Date Filing Date
US14/006,258 Abandoned US20140011089A1 (en) 2011-03-25 2012-03-26 Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method
US15/813,734 Abandoned US20180076461A1 (en) 2011-03-25 2017-11-15 Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method

Family Applications After (1)

Application Number Title Priority Date Filing Date
US15/813,734 Abandoned US20180076461A1 (en) 2011-03-25 2017-11-15 Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method

Country Status (6)

Country Link
US (2) US20140011089A1 (fr)
EP (1) EP2690123B1 (fr)
JP (1) JP5821137B2 (fr)
KR (1) KR101620675B1 (fr)
CN (1) CN103429640B (fr)
WO (1) WO2012132396A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150228980A1 (en) * 2014-02-12 2015-08-13 GM Global Technology Operations LLC High performance silicon electrodes having improved interfacial adhesion between binder and silicon
US20160059535A1 (en) * 2014-08-29 2016-03-03 Materion Corporation Conductive bond foils
US9531004B2 (en) 2013-12-23 2016-12-27 GM Global Technology Operations LLC Multifunctional hybrid coatings for electrodes made by atomic layer deposition techniques
US9685654B2 (en) * 2014-04-18 2017-06-20 Ube Industries, Ltd. Method for producing electrode
US10103384B2 (en) 2013-07-09 2018-10-16 Evonik Degussa Gmbh Electroactive polymers, manufacturing process thereof, electrode and use thereof
US10164245B2 (en) 2016-09-19 2018-12-25 GM Global Technology Operations LLC High performance silicon electrodes having improved interfacial adhesion between binder, silicon and conductive particles
US10396360B2 (en) 2016-05-20 2019-08-27 Gm Global Technology Operations Llc. Polymerization process for forming polymeric ultrathin conformal coatings on electrode materials
US10662555B2 (en) 2016-03-31 2020-05-26 I.S.T. Corporation Polyimide fiber and method for producing polyimide fiber
US10756350B2 (en) * 2016-07-22 2020-08-25 Samsung Electronics Co., Ltd. Binder, method of preparing the binder, and anode and lithium battery including the binder
US10868307B2 (en) 2018-07-12 2020-12-15 GM Global Technology Operations LLC High-performance electrodes employing semi-crystalline binders
US10899886B2 (en) * 2016-09-23 2021-01-26 Lg Chem, Ltd. Polyimide precursor solution and method for producing same
US11228037B2 (en) 2018-07-12 2022-01-18 GM Global Technology Operations LLC High-performance electrodes with a polymer network having electroactive materials chemically attached thereto

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013099558A1 (fr) * 2011-12-26 2013-07-04 三洋電機株式会社 Procédé de production d'électrode négative pour batteries secondaires au lithium, électrode négative pour batteries secondaires au lithium, et batterie secondaire au lithium
KR101633278B1 (ko) * 2015-01-13 2016-06-24 주식회사 피엔에스테크놀로지 리튬 이차전지의 음극 활물질용 바인더 조성물 및 이로부터 형성된 음극 활물질 조성물과 리튬 이차전지
JP6111453B2 (ja) * 2015-02-26 2017-04-12 株式会社アイ．エス．テイ ポリイミドコーティング活物質粒子、電極材料用スラリー、負極、電池、及び、ポリイミドコーティング活物質粒子の製造方法
JPWO2016152505A1 (ja) * 2015-03-25 2017-12-07 株式会社村田製作所 リチウムイオン二次電池
JP2017059527A (ja) 2015-09-14 2017-03-23 日本合成化学工業株式会社 二次電池電極用バインダー組成物、二次電池電極、及び二次電池
JP6974800B2 (ja) * 2016-08-24 2021-12-01 日産化学株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
CN106784838A (zh) * 2016-11-28 2017-05-31 德阳九鼎智远知识产权运营有限公司 一种锂电池负极材料及其锂电池
CN110521038B (zh) 2017-04-19 2021-06-29 日本A&L株式会社 电极用粘合剂、电极用组合物和电极
CN107248452B (zh) * 2017-06-02 2018-10-16 大连理工大学 一种超快氢离子复合电极材料及其制备方法
CN111263992B (zh) * 2018-10-03 2023-06-16 杰富意化学株式会社 糊料组合物、二次电池用电极材料、二次电池用电极及二次电池
CN109880091A (zh) * 2019-02-26 2019-06-14 中国科学院化学研究所 一种半芳香族热固性聚酰亚胺树脂及其制备方法与用途
CN111200128B (zh) * 2020-03-12 2022-09-13 河南电池研究院有限公司 一种抑制锂离子电池正极材料过渡金属离子溶出的正极材料的制备方法
CN111403745A (zh) * 2020-03-26 2020-07-10 北京化工大学常州先进材料研究院 一种锂离子电池用耐高温粘合剂及应用该粘合剂的电池极片
CN111900387B (zh) * 2020-07-28 2022-05-17 宁波锋成先进能源材料研究院 水系电池极片材料、水系电池极片及其制备方法与应用
CN115176361A (zh) * 2020-11-27 2022-10-11 株式会社Lg化学 用于二次电池的阳极的粘合剂、二次电池的阳极和二次电池

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3533997A (en) * 1969-05-28 1970-10-13 Du Pont Crosslinkable polyamide-acids and polyimides and crosslinked polymeric products made therefrom
US4759987A (en) * 1985-06-05 1988-07-26 Nitto Electric Industrial Co., Ltd. Polyimide powder and process for producing the same
US20050244711A1 (en) * 2002-06-26 2005-11-03 Atsushi Fukui Negative electrode for lithium secondary cell and lithium secondary cell
US20060099506A1 (en) * 2004-11-08 2006-05-11 3M Innovative Properties Company Polyimide electrode binders
US20080124631A1 (en) * 2006-06-30 2008-05-29 Sanyo Electric Co., Ltd. Lithium secondary battery and method of manufacturing the same
US20080193831A1 (en) * 2007-02-14 2008-08-14 Samsung Sdi Co., Ltd. Anode active material, method of preparing the same, anode and lithium battery containing the material
US20090246632A1 (en) * 2008-03-28 2009-10-01 Atsushi Fukui Lithium secondary battery and method of manufacturing the same

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59204609A (ja) * 1983-05-04 1984-11-20 Showa Electric Wire & Cable Co Ltd ポリアミドイミド系樹脂組成物
JP2000007783A (ja) * 1998-06-23 2000-01-11 Hitachi Chemical Dupont Microsystems Ltd ポリイミド前駆体樹脂組成物及びその製造方法
EP1013650B1 (fr) * 1998-10-30 2007-01-24 Hitachi Chemical DuPont MicroSystems Ltd. Dianhydride tétracarboxylique, dérivé et sa préparation, précurseur de polyimide, polyimide, composition de résine, composition de résine photosensible, procédé de formation d'une configuration en relief, et élément électronique
JP4560859B2 (ja) * 1998-10-30 2010-10-13 日立化成デュポンマイクロシステムズ株式会社 テトラカルボン酸二無水物、その誘導体及び製造法、ポリイミド前駆体、ポリイミド、樹脂組成物、感光性樹脂組成物、レリーフパターンの製造法、並びに電子部品
JP2000273172A (ja) * 1999-03-19 2000-10-03 Hitachi Chemical Dupont Microsystems Ltd ポリアミド酸エステル、その製造法、感光性樹脂組成物、それを用いたパターン製造法及び電子部品
JP2001194796A (ja) * 1999-10-29 2001-07-19 Hitachi Chemical Dupont Microsystems Ltd ポジ型感光性樹脂組成物、パターンの製造法及び電子部品
JP4250841B2 (ja) * 1999-12-20 2009-04-08 日立化成デュポンマイクロシステムズ株式会社 ポジ型感光性樹脂組成物、パタ−ンの製造法および電子部品
JP4507894B2 (ja) * 2005-01-24 2010-07-21 宇部興産株式会社 非対称中空糸ガス分離膜、及びガス分離方法
CN101437984A (zh) * 2006-05-17 2009-05-20 株式会社Pi技术研究所 金属复合膜及其制造方法
JP5129230B2 (ja) * 2007-10-26 2013-01-30 旭化成イーマテリアルズ株式会社 感光性樹脂組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3533997A (en) * 1969-05-28 1970-10-13 Du Pont Crosslinkable polyamide-acids and polyimides and crosslinked polymeric products made therefrom
US4759987A (en) * 1985-06-05 1988-07-26 Nitto Electric Industrial Co., Ltd. Polyimide powder and process for producing the same
US20050244711A1 (en) * 2002-06-26 2005-11-03 Atsushi Fukui Negative electrode for lithium secondary cell and lithium secondary cell
US20060099506A1 (en) * 2004-11-08 2006-05-11 3M Innovative Properties Company Polyimide electrode binders
US20080124631A1 (en) * 2006-06-30 2008-05-29 Sanyo Electric Co., Ltd. Lithium secondary battery and method of manufacturing the same
US20080193831A1 (en) * 2007-02-14 2008-08-14 Samsung Sdi Co., Ltd. Anode active material, method of preparing the same, anode and lithium battery containing the material
US20090246632A1 (en) * 2008-03-28 2009-10-01 Atsushi Fukui Lithium secondary battery and method of manufacturing the same

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10103384B2 (en) 2013-07-09 2018-10-16 Evonik Degussa Gmbh Electroactive polymers, manufacturing process thereof, electrode and use thereof
US9531004B2 (en) 2013-12-23 2016-12-27 GM Global Technology Operations LLC Multifunctional hybrid coatings for electrodes made by atomic layer deposition techniques
US20150228980A1 (en) * 2014-02-12 2015-08-13 GM Global Technology Operations LLC High performance silicon electrodes having improved interfacial adhesion between binder and silicon
US9564639B2 (en) * 2014-02-12 2017-02-07 GM Global Technology Operations LLC High performance silicon electrodes having improved interfacial adhesion between binder and silicon
US9685654B2 (en) * 2014-04-18 2017-06-20 Ube Industries, Ltd. Method for producing electrode
US20160059535A1 (en) * 2014-08-29 2016-03-03 Materion Corporation Conductive bond foils
US10662555B2 (en) 2016-03-31 2020-05-26 I.S.T. Corporation Polyimide fiber and method for producing polyimide fiber
US10991946B2 (en) 2016-05-20 2021-04-27 GM Global Technology Operations LLC Polymerization process for forming polymeric ultrathin conformal coatings on electrode materials
US10396360B2 (en) 2016-05-20 2019-08-27 Gm Global Technology Operations Llc. Polymerization process for forming polymeric ultrathin conformal coatings on electrode materials
US10756350B2 (en) * 2016-07-22 2020-08-25 Samsung Electronics Co., Ltd. Binder, method of preparing the binder, and anode and lithium battery including the binder
US10164245B2 (en) 2016-09-19 2018-12-25 GM Global Technology Operations LLC High performance silicon electrodes having improved interfacial adhesion between binder, silicon and conductive particles
US10899886B2 (en) * 2016-09-23 2021-01-26 Lg Chem, Ltd. Polyimide precursor solution and method for producing same
US10868307B2 (en) 2018-07-12 2020-12-15 GM Global Technology Operations LLC High-performance electrodes employing semi-crystalline binders
US11228037B2 (en) 2018-07-12 2022-01-18 GM Global Technology Operations LLC High-performance electrodes with a polymer network having electroactive materials chemically attached thereto

Also Published As

Publication number Publication date
KR20130135951A (ko) 2013-12-11
EP2690123B1 (fr) 2017-03-01
EP2690123A1 (fr) 2014-01-29
CN103429640B (zh) 2016-03-02
CN103429640A (zh) 2013-12-04
WO2012132396A1 (fr) 2012-10-04
JP5821137B2 (ja) 2015-11-24
EP2690123A4 (fr) 2014-11-19
KR101620675B1 (ko) 2016-05-12
JPWO2012132396A1 (ja) 2014-07-24
US20180076461A1 (en) 2018-03-15

Similar Documents

Publication Publication Date Title
US20180076461A1 (en) Polyimide precursor solution, polyimide precursor, polyimide resin, mixture slurry, electrode, mixture slurry production method, and electrode formation method
EP3264504B1 (fr) Suspension épaisse pour matériau d'électrode et son procédé de fabrication, électrode négative, batterie, et particules de matériau actif enrobées de polyimide
JP6448681B2 (ja) リチウム二次電池負極およびその製造方法
JP6217647B2 (ja) 双極型リチウムイオン二次電池用集電体および双極型リチウムイオン二次電池
JP5761740B2 (ja) 電極、および電極形成方法
JP5598821B2 (ja) 負極用バインダー組成物および負極用合剤スラリー
EP2594609A1 (fr) Composition de solution aqueuse de précurseur de polyimide et procédé d'obtention de composition de solution aqueuse de précurseur de polyimide
JP5946444B2 (ja) ポリイミド系樹脂微粒子の複合体膜およびその用途
TW201636412A (zh) 鋰二次電池之電極用黏結劑樹脂、鋰二次電池用電極及鋰二次電池
JP2013077498A (ja) リチウムイオン二次電池用負極及びその製造方法
JPWO2018105338A1 (ja) 蓄電素子用バインダー組成物、蓄電素子用スラリー組成物、電極、電極の製造方法、二次電池および電気二重層キャパシタ
JP5543826B2 (ja) 二次電池用負極及びこれを用いた二次電池
JP2023113663A (ja) 電極
JP7144794B2 (ja) リチウムイオン二次電池製造用バインダー及びこれを用いたリチウムイオン二次電池
JP2013175316A (ja) リチウムイオン二次電池およびそれを搭載する車両
JP2014029802A (ja) 電極用合剤スラリーおよび電極

Legal Events

Date Code Title Description
AS Assignment

Owner name: I.S.T. CORPORATION, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YAMADA, HIROSHI;SAWA, KAZUKI;NIMURA, YOSHIHITO;AND OTHERS;SIGNING DATES FROM 20130820 TO 20130903;REEL/FRAME:031243/0459

Owner name: NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YAMADA, HIROSHI;SAWA, KAZUKI;NIMURA, YOSHIHITO;AND OTHERS;SIGNING DATES FROM 20130820 TO 20130903;REEL/FRAME:031243/0459

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION